Anthracene compound and process of making it.



lUNllTElD taTATlES PATENT OFFICE,

MAX HENRY ISLER, 0F MANNHEIM, AND HUGO WOLFE, OF LUDWIGSHAFEN-ON-THE- RHINE, GERMANY, ASSIGNORS TO BADISCHE ANILIN & SODA FABRIK, OF LUDWIGS- HAFlEN-ON-THE-RHINE, GERMANY, A CORPORATION.

ANTHRACENE COMPOUND AND PROCESS OF MAKING 1T.

No Drawing.

To all whom it may concern:

Be it known that we, MAX HENRY IsLnn, chemist, and HUGO WOLFE, doctor of philosophy and chemist, being respectively a citizen of the Swiss Republic and a subject of the Grand Duke of Baden, and residing at Mannheim and Ludwigshafen-on-the-Rhine, Germany, respectively, have invented new and useful Improvements in Anthracene Compounds and Processes of Making Them, of which the following is a specification.

In the specification of Letters Patent No. 863,397 is described the production of coloring matters of the anthraquinone series, namely, those in which three anthraquinone groups are joined together .by means of nitrogen, and these compounds are there termed dianthraquinonyl diamino anthraquinone compounds. The said patent claims generically these new compounds and a process of making them. In the present application we make no generic claim to such products or the process of making them, but

we wish to describe and claim specifically certain compounds and the process of making such compounds which are not specifically described in the said Letters Patent.

We have descovered that coloring matters which are not specifically described in the aforesaid Letters Patent are obtained by condensing beta beta dihalogen-anthraquinone with a l-amino-anthraquinone derivative which is substituted in the ring not con-' taining the amino group by a substituent which does not react with, that is to say, is

a neutral with respect to, the dihalogen-am one another, and hereby also obtain 9 thraquinone employed, or by condensing alpha alpha diamino anthraquinone with a beta halogen anthraquinone derivative which is substituted in the ring not containing the halogen atom by a substituent which does not react with, that is to say, is neutral with respect to, the alpha alpha 4 diaminoanthraquinone employed, (for the purposes of this invention these processes are equ valent). Or, we can condense 1 amino 6- halogen anthraquinone, or 1-amino-7-halogen-anthraquinone, either with itself or with similar compounds, and for the purposes of this invention these processes are e uivalent.

As instances of the substltut-ed l-amino- Specificationof Letters Patent.

Patented June Ml, 191(0).

Application filed February 16, 1909. Serial No. 478,313.

anthraquinone and beta-halogen-anthraquinone compounds which we can employ according to our invention, we mention for instance l-amino-fi-halogen-anthraquinone, 1- amino 7 halogen anthraquinone, and also those containing either the NHR, the Nli the OH, or the OR group (where R represents either an alkyl, or an aryl, group), and also those derivatives of l-amino-anthraquinone to which an additional ring (for instance the pyridin ring) has been joined.

In particular, in this application we desire to be understood as claiming the production of coloring matters by condensing beta-beta-dihalogen-anthraquinone with 1- amino-betahalogen-anthraquinone in which the amino group and the halogen atom are attached to diflerent rings of the anthraquinone residue, such as l-aminosfi-chlor-anv thraquinone and 1 amino 7 chlor anthraquinone. The coloring matters so produced possess the generic properties of the coloring matters claimed in the aforesaid Patent No. 863397, that is to say, in the unsulfonated form they are insoluble in water andin dilute acids and alkalies, dificultly soluble in most organic solvents, soluble in concentrated sulfuric acid yielding greenish solutions, which solutions upon warming turn bluer, and arealso' soluble'in alkaline hydrosulfite solutions yielding yellowish red to brownred vats, dyeing cotton substantially red shades.

lhe new coloring matters obtained by condensing beta-beta-dihalogen-anthraquinone with l-amino-beta-halogen-anthraquinone in which the amino group and the halogen atom are attached to dilferent rings of the anthraquinone residue can be distinguished from the coloring matters specifically claimed in the aforesaid specification in that the said new coloring matters possess a composition corresponding to the presence of two atoms of halogen 1n the molecule, 2'. 6., if the chlorin derivatives be employed, the coloring matters produced contain, in the pure state, over nine per cent. of chlorin or, if the bromin derivatives 'be employe the coloring matters contain over nineteen per cent. of bromin.

The following examples will serve to illus how it can be carried 1nto practical effect, but our invention 1s not confined to these 4 examples. The parts are by weight.

Example 1. Boil together for from four, to eight, hours, fifteen parts of 1-amino-6- chlor-anthraquinone, one hundred and fifty parts of nitrobenzene, four parts of calcined sodium carbonate and three-tenths of a part of copper oxid. When the melt is cold, filter 011" the coloring matter and Wash it with alcohol. It can be obtained in the form of a paste by dissolving it in concentrated sulfuric acid, precipitating by means of water, and filtering. In a similar manner, coloring matter can be obtained from 1-amino-7- chlor-anthraquinone, or from a mixture of lamino-6-chlor-anthraquinone with 1-aminoof a part of copper oxid. When the forma- Solution in: p i Dyes cotton from Condensation productirom: v Boiling nitro- Conc. sulfuric Cone. sulfuric hydmsumw L -benezene. acid. acid+boric acid.

.ianilnoj-o-chloranthmquinonewithitself.........; Yellow-red...... Olive-greau....'. Blue-violet Bordeauxred.

l-aminoJ-chloranthraquinone with itself Brown-red G Violet-blue Yellow-red. l-amino-o-chloranthraquinone+l-amino-7-chlor-anthmquinone.. Yellow-red ..do ..do Yellowish red. 1-amino-6-ch1omnthraquinone+1.5diamino-anthraquinone Y%llow1-l;d,(di{- .....do Blue Bluish red. on y so- Y uble. l-amino-ochloi'anthmquinone+1.8-diamino-anthxaquinone Reddish blue... Blue-red. 1-amino-7-chloranthmquinone+l.5Fdlamino-anthraquinona... lue Yellowish red. l-amino-7-chloranthraquinone+1.8-diaminwmthraquinona. Greenablue do. l-amino-o-chlomnthmquinone+2.6-dichlonanthraquinone.m. Violet Bordeauxred. 1-amino-&chlomnthraquinone+2.7-dichlor-anthraquinone Blue-violet o.

1-amino-7-chlomnthraquinone+2.6d1chlor-anthmquinone Blue Yellow-red.

v1-amino-7-chloranthmquinone+2.7-dichior-anth1aquinone.. ..do ..;-:do .-do..... do.

tion of coloring matter is complete, work up the product as described in the foregoing Example 1.

Example 4: Boil together five and threefifths parts of 2.6-dichlor-anthraquinone, ten parts of 1-amino-6-methyl-amino-anthraquinone, one hundred and sixty parts of nitrobenzene, two-fifths of a part of copper oxid and four parts of calcined soda. When the formation of the coloring matter is. complete, allow the mass to cool, and filter off the coloring matter and wash it with alcohol.

In this example 2.7-dichlor-anthraquinone can be employe instead of 2.6-dichlor-anthraquinone, and, instead of l-amino-6- Y methyl-amino-anthraquinone, other derivatives can be used, such as 1-amino-7-alkyl- 5o Example 5: Boil together twelve parts of 0 1.5 diamino anthraquinone, twenty seven parts of 2-chlor 5-methyl amino anthra quinone, four hundred parts of nitrobenzene, one part of copper oxid, and ten parts ofcalcined soda, and work up the product 5 as described in the foregoing example. In this fifth example, 1.8-diamino-anthraquinone can be employed instead of 1.5- diaminoanthraquinone, and, instead ofv 2 chlor 5 methyl amino-anthraquinone,

other derivatives can be used, such as 8 methyl amino-2-chlor-anthraquinone, 5- hydroxy-2-chlor-anthraquinone (obtainable by boiling diazotized 5 amino- 2 chloranthraquinone), 8-hydroxy-2-chlor-anthraquinone, 8 methoxy-2-chlor anthraquinone, 5 dimethylamino 2 chlor anthraquinone (obtainable from 2-chlor 5 nitro anthraquinone by means of dimethylamin) 8- dialkyl amino 2 chlor anthraquinone, 5-

nitro-2-chlor-anthraquinone, 8-nitro-2-chloranthraquinone, 5-acetamino-2-chlor-anthraquinone, and 8-acetamino-2-chlor-anthraquinone.

In the foregoing examples, other indifferent solvents can be employed instead of nitrobenzene, and the copper oxid can be replaced by metallic copper, or by aco per salt, and calcined soda canbe replace by calcium hydrate, sodium acetate, or potassium carbonate.

The following table gives some roperties of some of the coloring matters 0 tamable according to this invention:

and l-amino-an- 55 Now what we claim is:

1. The process of producing coloring matters of the anthracene series by condensing beta-beta-dihalogen-anthraquinone with a l-amino-anthraquinone derivative which is substituted in the ring different to that containing the amino group by a substituent which is neutral with respect to the dihalogen-anthraquinone employed substantially as described.

2. The process of producing coloring matters of the anthracene series by condensing l-amino 6 halogen-anthraquinone with alpha-amino-beta-halogen-anthraquinone substantially as described.

3. The process of producing coloring matters of the anthracene series by condensing l-amino-6-halogen-anthraquinone with itself substantially as described.

4. The process of producing coloring matters of the anthracene series by condensing beta-beta-dihalogen-anthraquinone with 1- amino-beta-halogen-anthraquinone in which the amino group and the halogen atom are attached to difi'erent rings of the anthraquinone residue substantially as described.

5. The process of producing coloring matters of the anthracene series by condensing beta-beta dichlor anthraquinone with 1- amino-beta-chlor-anthraquinone in which the amino grou and the halogen atom are attached to di erent rings of the anthraquinone residue substantially as described.

6. The process of producing coloring matters of the anthracene series by condensing one molecular proportion of 2.6-dichloranthra uinone with two molecular proportions 0 1.6-amino-chlor-anthraquinone substantially as described.

7. As new articles of manufacture dihalogenated dianthraquinonyl-diamino-anthraquinone compounds which in the unsulfonated form are insoluble in water and in dilute acids and alkalies, diflicultly soluble in most organic solvents, soluble in concentrated sulfuric acid yielding greenish solutions which solutions upon warming turn bluer, and are also soluble in alkaline hydrosulfite solutions yielding yellowish red to brown-red vats dyeing cotton substantively red shades, and which contain more than nine per cent. of halogen.

8. As new articles of manufacture dichlorinated quinone compounds which can be obtained by condensing one molecular proportion of 2.6-dichlor-anthra uinone with two molecular proportions o 1.6-amino-chlor-anthraquinone, which in the unsulfonated form are insoluble in water and in dilute acids and alkalies, diflicultly soluble in most organic solvents, soluble in concentrated sulfuric acid yielding greenish solutions which solutions upon warming turn bluer, and are also soluble in alkaline hydrosulfite solutions yielding yellowish red to brownred vats dyeing cotton substantively red shades, and which contain more than nine per cent. of chlorin.

In testimony whereof we have hereunto dianthraquinonyl diamino anthra set our hands in the presence of two subscribing witnesses.

MAX HENRY ISLE'R. HUGO WOLFF.

Witnesses:

J. Ame. LLOYD, Jos. H. LEUTE. 

